CN104356031A - Di-n-octyl sodium sulfonate itaconate and preparation method thereof - Google Patents
Di-n-octyl sodium sulfonate itaconate and preparation method thereof Download PDFInfo
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- succinic acid
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- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 title claims abstract description 224
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims abstract description 52
- 238000005886 esterification reaction Methods 0.000 claims abstract description 50
- 238000006277 sulfonation reaction Methods 0.000 claims abstract description 44
- 230000032050 esterification Effects 0.000 claims abstract description 42
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 35
- 239000011734 sodium Substances 0.000 claims abstract description 35
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 35
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims abstract description 26
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims abstract description 26
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims abstract description 26
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- 239000000047 product Substances 0.000 claims description 44
- UMTVCEDYAZNYBU-UHFFFAOYSA-N 2-methylidenebutanedioic acid;sodium Chemical compound [Na].OC(=O)CC(=C)C(O)=O UMTVCEDYAZNYBU-UHFFFAOYSA-N 0.000 claims description 39
- 239000003054 catalyst Substances 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 29
- 230000002378 acidificating effect Effects 0.000 claims description 28
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 20
- 238000001816 cooling Methods 0.000 claims description 19
- 230000000694 effects Effects 0.000 claims description 19
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 13
- 230000035484 reaction time Effects 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- 239000002244 precipitate Substances 0.000 claims description 10
- 238000007710 freezing Methods 0.000 claims description 9
- 230000008014 freezing Effects 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 239000003921 oil Substances 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 230000001020 rhythmical effect Effects 0.000 claims description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 14
- 230000015572 biosynthetic process Effects 0.000 abstract description 8
- 238000003786 synthesis reaction Methods 0.000 abstract description 8
- 150000002148 esters Chemical class 0.000 abstract description 6
- 239000003444 phase transfer catalyst Substances 0.000 abstract description 6
- 239000004094 surface-active agent Substances 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000314 lubricant Substances 0.000 abstract description 2
- 239000003377 acid catalyst Substances 0.000 abstract 1
- 235000014113 dietary fatty acids Nutrition 0.000 abstract 1
- 229930195729 fatty acid Natural products 0.000 abstract 1
- 239000000194 fatty acid Substances 0.000 abstract 1
- 150000004665 fatty acids Chemical class 0.000 abstract 1
- 239000003112 inhibitor Substances 0.000 abstract 1
- 230000000149 penetrating effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 25
- -1 papermaking Substances 0.000 description 13
- RNMDNPCBIKJCQP-UHFFFAOYSA-N 5-nonyl-7-oxabicyclo[4.1.0]hepta-1,3,5-trien-2-ol Chemical compound C(CCCCCCCC)C1=C2C(=C(C=C1)O)O2 RNMDNPCBIKJCQP-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 5
- 229960004756 ethanol Drugs 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 229960000935 dehydrated alcohol Drugs 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 150000002191 fatty alcohols Chemical class 0.000 description 4
- DUIOKRXOKLLURE-UHFFFAOYSA-N 2-octylphenol Chemical compound CCCCCCCCC1=CC=CC=C1O DUIOKRXOKLLURE-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- DTPCFIHYWYONMD-UHFFFAOYSA-N decaethylene glycol Polymers OCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO DTPCFIHYWYONMD-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- MQVMJSWYKLYFIG-UHFFFAOYSA-N propane-1-sulfonic acid;sodium Chemical compound [Na].CCCS(O)(=O)=O MQVMJSWYKLYFIG-UHFFFAOYSA-N 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000007039 two-step reaction Methods 0.000 description 2
- RZXLPPRPEOUENN-UHFFFAOYSA-N Chlorfenson Chemical compound C1=CC(Cl)=CC=C1OS(=O)(=O)C1=CC=C(Cl)C=C1 RZXLPPRPEOUENN-UHFFFAOYSA-N 0.000 description 1
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical class [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- WSNSMPZJJIYZCV-UHFFFAOYSA-N [Na]C Chemical compound [Na]C WSNSMPZJJIYZCV-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- OGVXYCDTRMDYOG-UHFFFAOYSA-N dibutyl 2-methylidenebutanedioate Chemical compound CCCCOC(=O)CC(=C)C(=O)OCCCC OGVXYCDTRMDYOG-UHFFFAOYSA-N 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- ZWWQRMFIZFPUAA-UHFFFAOYSA-N dimethyl 2-methylidenebutanedioate Chemical compound COC(=O)CC(=C)C(=O)OC ZWWQRMFIZFPUAA-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 238000012262 fermentative production Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000002455 scale inhibitor Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses di-n-octyl sodium sulfonate itaconate and a preparation method thereof. Itaconic acid, sodium bisulfite and n-octanol are taken as raw materials, and the di-n-octyl sodium sulfonate itaconate is prepared by performing sulfonation reaction and esterification reaction under the action of a polymerization inhibitor and an acid catalyst respectively. The molecular structure of the di-n-octyl sodium sulfonate itaconate is shown in the Specification. Compared with a conventional preparation process for a fatty acid ester sodium sulfonate surfactant, an adopted esterification-after-sulfonation synthesis process has the advantages that the problem of insolubility of two phases, i.e. an esterification product (oil-soluble) and a sulfonation agent (water-soluble) in a sulfonation reaction process is successfully solved, the sulfonation reaction process and an esterification reaction process can both be implemented in a homogeneous phase system, the use of a phase transfer catalyst in the conventional process is avoided, a production process route is simplified, and the purity and yield of a product are improved; the di-n-octyl sodium sulfonate itaconate product prepared by the synthesis process is high in yield, and can be used as a lubricant, a penetrating agent and the like.
Description
Technical field
The invention belongs to novel surfactant technical field, more particularly relate to the proposition of a kind of methylene-succinic acid di-n-octyl sulfonate sodium tensio-active agent and preparation method thereof.
Background technology
Methylene-succinic acid is a kind of important organic acid, is the reproducible industrial chemicals of one obtained through fermentative production by W-Gum.The molecular structure of methylene-succinic acid determines its chemical property very vivaciously, can be widely used in many fields such as synthetic resins, rubber, chemical fibre, papermaking, medicine and food.
2002, Yu Shitao etc. with methylene-succinic acid and methyl alcohol for raw material has synthesized dimethyl itaconate under catalyst action; Chinese patent ZL 2,009 10231146.6 and ZL 200910231145.1 individually discloses the preparation method of dibutyl itaconate and diisooctyl itaconate; Chinese Patent Application No. 201210482578.6 discloses a kind of High-molecular weight polyitaconic acid butanediol and preparation method thereof.Chinese patent ZL 03112046.6 discloses a kind of methylene-succinic acid, (methyl) Sodium allyl sulphonate and (methyl) crylic acid hydroxy ester and obtain itaconic acid copolymer and preparation method thereof through aqueous solution polymerization under catalyst action, and this multipolymer is mainly as the Scale inhibitors in water treatment industry and clean-out system.At present, methylene-succinic acid is mainly used in synthesizing ester derivative and multipolymer thereof, and is that the research report of main raw material synthetic surfactant is less with methylene-succinic acid.
2005, Prasath etc. utilized itaconic anhydride to carry out esterification with 1-dodecyl alcohol and 1-hexadecyl alcohol respectively to synthesize itaconic ester class polymerizable nonionogenic tenside methylene-succinic acid list dodecyl ester and methylene-succinic acid list cetyl ester.Research finds, if substitute itaconic anhydride with methylene-succinic acid, even if under an acidic catalyst existent condition, esterification gained productive rate is not high yet.2012, wearing Dongming etc. was starting raw material with methylene-succinic acid, has synthesized methylene-succinic acid monoester fatty alcohol propyl sulfonic acid sodium: (1) methylene-succinic acid Dehydration is for itaconic anhydride through following four-step reaction; (2) itaconic anhydride and fatty alcohol direct esterification obtain methylene-succinic acid monoester fatty alcohol; (3) methylene-succinic acid monoester fatty alcohol and NaOH neutralize and obtain methylene-succinic acid monoester fatty alcohol sodium salt; (4) methylene-succinic acid monoester fatty alcohol sodium salt and l, 3-N-morpholinopropanesulfonic acid lactone reaction obtains methylene-succinic acid list ten diester propyl sulfonic acid sodium.Its essence is still that raw material carries out esterification and sulfonation reaction with itaconic anhydride.2010, Chinese patent (application number 201010623695.0) disclosed a kind of octylphenol polyoxyethylene ether itaconic acid monoester sulfonic acid disodium salt and preparation method thereof.Be catalyzer with the vitriol oil, utilize methylene-succinic acid to carry out esterification modification to nonionogenic tenside octyl phenol polyoxyethylene (10) ether, obtain octyl phenol polyoxyethylene (10) ether methylene-succinic acid monoesters; Then, in esterification products, add the aqueous solution of S-WAT, after isothermal reaction for some time, obtain sulfonated products octyl phenol polyoxyethylene (10) ether methylene-succinic acid monoesters disodium sulfonate salt.2011, Ding etc. with methylene-succinic acid, polyoxyethylene nonylphenol ether (10) and S-WAT for raw material, under the effect of the vitriol oil, polyoxyethylene nonylphenol ether (10) methylene-succinic acid monoester disodium salt and polyoxyethylene nonylphenol ether (10) methylene-succinic acid dibasic acid esters sodium salt are synthesized through esterification and sulfonation reaction.
Above-mentioned with methylene-succinic acid and derivative thereof for raw material is prepared in the example of methylene-succinic acid based surfactants, the synthesis route of sulfonation after the first esterification of most employing, due to the problem that esterification products (oil soluble) in sulfonation reaction process and sulphonating agent (water-soluble) two-phase are immiscible, namely the sulfonation process of itaconic ester is an inhomogeneous reaction process, need to add phase-transfer catalyst to improve the yield of sulfonation reaction, or in the process preparing dibasic acid esters, retain the phase-transfer catalyst that a small amount of monoesters is used as Subsequent sulfonation reaction, but above-mentioned two kinds of ways all can cause the content of impurity in product to increase, affect purity and the yield of product.The present invention take methylene-succinic acid as starting raw material, and the synthesis technique of esterification after employing earlier sulfonation, makes two-step reaction all complete in homogeneous system, avoid the use of phase-transfer catalyst, simplify production process route, improve product purity and yield.
Summary of the invention
An object of the present invention is to provide a kind of novel methylene-succinic acid di-n-octyl sulfonate sodium, has following molecular structure:
.
Another object of the present invention is to provide the preparation method, the particularly preparation method of methylene-succinic acid di-n-octyl sulfonate sodium of the itaconic ester sulfonate sodium of esterification after a kind of earlier sulfonation.
Its preparation method is solvent with water, is stopper, is that sulphonating agent carries out sulfonation to methylene-succinic acid, obtains sulfonated products methylene-succinic acid sodium sulfonate solution with sodium bisulfite with Resorcinol, after being separated, purifying, obtain methylene-succinic acid sodium sulfonate white powder; Again under the effect of an acidic catalyst, adopt n-Octanol and methylene-succinic acid sodium sulfonate to carry out esterification, after cooling, obtain methylene-succinic acid di-n-octyl sulfonate sodium through washing with alcohol.
Its material proportion is:
1) mass ratio of sodium bisulfite and methylene-succinic acid is 0.8/1 ~ 1.0/1;
2) mass ratio of hydroquinone of polymerization retarder and methylene-succinic acid is 0.01% ~ 0.1%;
3) mass ratio of an acidic catalyst and methylene-succinic acid is 1.0% ~ 5.0%;
4) mass ratio of n-Octanol and methylene-succinic acid sodium sulfonate is 1.1/1 ~ 2.5/1.
Its preparation technology adopts rhythmic reaction mode, take water as solvent, under the effect of stopper, methylene-succinic acid and sodium bisulfite is made to carry out sulfonation reaction, sulfonation reaction temperature controls between 80 ~ 120 DEG C, and the sulfonation reaction time is 3.0 ~ 6.0h, obtains sulfonated products methylene-succinic acid sodium sulfonate solution; Cooling, adds ethanol, then carries out freezing treatment to solution, obtain white precipitate in above-mentioned solution, for subsequent use after filtration, drying; Again under the effect of an acidic catalyst, methylene-succinic acid sodium sulfonate and n-Octanol is made to carry out esterification, esterification reaction temperature 110 ~ 180 DEG C, reaction time of esterification is 2.0 ~ 6.0h, after esterification completes cooling, obtain product methylene-succinic acid di-n-octyl sulfonate sodium by washing with alcohol, product ultimate yield is 90.0% ~ 98.5%.
Described an acidic catalyst is the vitriol oil, hydrochloric acid, phosphoric acid, tosic acid.
The invention has the advantages that:
(1) methylene-succinic acid di-n-octyl sulfonate sodium provided by the invention is a kind of novel methylene-succinic acid esters surface active agent, its main raw material methylene-succinic acid produces acquisition by reproducible W-Gum through biological fermentation, greatly reduces the dependence of Surfactant Industry to petrochemical materials.
(2) the present invention adopts the synthesis route of esterification after earlier sulfonation, avoids the problem that itaconic ester and sulphonating agent in traditional synthesis are immiscible, eliminates the use of phase-transfer catalyst, the purity of product and yield are greatly improved.
Embodiment
embodiment 1
A kind of methylene-succinic acid di-n-octyl sulfonate sodium, it be a kind of with methylene-succinic acid, sodium bisulfite and n-Octanol for raw material, respectively under the effect of stopper and an acidic catalyst, be prepared from through sulfonation reaction and esterification, there is following molecular structure:
.
Its preparation method is solvent with water, is stopper, is that sulphonating agent carries out sulfonation to methylene-succinic acid, obtains sulfonated products methylene-succinic acid sodium sulfonate solution with sodium bisulfite with Resorcinol, after being separated, purifying, obtain methylene-succinic acid sodium sulfonate white powder; Again under the effect of an acidic catalyst, adopt n-Octanol and methylene-succinic acid sodium sulfonate to carry out esterification, after cooling, obtain methylene-succinic acid di-n-octyl sulfonate sodium through washing with alcohol.
embodiment 2
The preparation method of methylene-succinic acid di-n-octyl sulfonate sodium, its material proportion is:
1) mass ratio of sodium bisulfite and methylene-succinic acid is 1.0/1;
2) mass ratio of hydroquinone of polymerization retarder and methylene-succinic acid is 0.05%;
3) mass ratio of an acidic catalyst and methylene-succinic acid is 1.0%;
4) mass ratio of n-Octanol and methylene-succinic acid sodium sulfonate is 2.5/1.
Its preparation technology adopts rhythmic reaction mode, take water as solvent, under the effect of stopper, methylene-succinic acid and sodium bisulfite is made to carry out sulfonation reaction, sulfonation reaction temperature controls between 80 ~ 120 DEG C, and the sulfonation reaction time is 3.0 ~ 6.0h, obtains sulfonated products methylene-succinic acid sodium sulfonate solution; Cooling, adds ethanol, then carries out freezing treatment to solution, obtain white precipitate in above-mentioned solution, for subsequent use after filtration, drying; Again under the effect of an acidic catalyst, methylene-succinic acid sodium sulfonate and n-Octanol is made to carry out esterification, esterification reaction temperature 110 ~ 180 DEG C, reaction time of esterification is 2.0 ~ 6.0h, cooling after esterification completes, obtain product methylene-succinic acid di-n-octyl sulfonate sodium by washing with alcohol, product ultimate yield is 90.0% ~ 98.5%.
Said an acidic catalyst is tosic acid.Remaining with embodiment 1.
embodiment 3
The preparation method of methylene-succinic acid di-n-octyl sulfonate sodium, its material proportion is:
1) mass ratio of sodium bisulfite and methylene-succinic acid is 0.8/1;
2) mass ratio of hydroquinone of polymerization retarder and methylene-succinic acid is 0.01%;
3) mass ratio of an acidic catalyst and methylene-succinic acid is 2.0%;
4) mass ratio of n-Octanol and methylene-succinic acid sodium sulfonate is 1.2/1.
Its preparation technology adopts rhythmic reaction mode, take water as solvent, under the effect of stopper, methylene-succinic acid and sodium bisulfite is made to carry out sulfonation reaction, sulfonation reaction temperature controls between 80 ~ 120 DEG C, and the sulfonation reaction time is 3.0 ~ 6.0h, obtains sulfonated products methylene-succinic acid sodium sulfonate solution; Cooling, adds ethanol, then carries out freezing treatment to solution, obtain white precipitate in above-mentioned solution, for subsequent use after filtration, drying; Again under the effect of an acidic catalyst, methylene-succinic acid sodium sulfonate and n-Octanol is made to carry out esterification, esterification reaction temperature 110 ~ 180 DEG C, reaction time of esterification is 2.0 ~ 6.0h, cooling after esterification completes, obtain product methylene-succinic acid di-n-octyl sulfonate sodium by washing with alcohol, product ultimate yield is 90.0% ~ 98.5%.
Said an acidic catalyst is the vitriol oil.Remaining with embodiment 1.
embodiment 4
The preparation method of methylene-succinic acid di-n-octyl sulfonate sodium, its material proportion is:
1) mass ratio of sodium bisulfite and methylene-succinic acid is 0.85/1;
2) mass ratio of hydroquinone of polymerization retarder and methylene-succinic acid is 0.1%;
3) mass ratio of an acidic catalyst and methylene-succinic acid is 5.0%;
4) mass ratio of n-Octanol and methylene-succinic acid sodium sulfonate is 1.1/1.
Its preparation technology adopts rhythmic reaction mode, take water as solvent, under the effect of stopper, methylene-succinic acid and sodium bisulfite is made to carry out sulfonation reaction, sulfonation reaction temperature controls between 80 ~ 120 DEG C, and the sulfonation reaction time is 3.0 ~ 6.0h, obtains sulfonated products methylene-succinic acid sodium sulfonate solution; Cooling, adds ethanol, then carries out freezing treatment to solution, obtain white precipitate in above-mentioned solution, for subsequent use after filtration, drying; Again under the effect of an acidic catalyst, methylene-succinic acid sodium sulfonate and n-Octanol is made to carry out esterification, esterification reaction temperature 110 ~ 180 DEG C, reaction time of esterification is 2.0 ~ 6.0h, cooling after esterification completes, obtain product methylene-succinic acid di-n-octyl sulfonate sodium by washing with alcohol, product ultimate yield is 90.0% ~ 98.5%.
Said an acidic catalyst is hydrochloric acid.Remaining with embodiment 1.
embodiment 5
The preparation method of methylene-succinic acid di-n-octyl sulfonate sodium, its material proportion is:
1) mass ratio of sodium bisulfite and methylene-succinic acid is 0.85/1;
2) mass ratio of hydroquinone of polymerization retarder and methylene-succinic acid is 0.03%;
3) mass ratio of an acidic catalyst and methylene-succinic acid is 2.5%;
4) mass ratio of n-Octanol and methylene-succinic acid sodium sulfonate is 1.1/1.
Its preparation technology adopts rhythmic reaction mode, take water as solvent, under the effect of stopper, methylene-succinic acid and sodium bisulfite is made to carry out sulfonation reaction, sulfonation reaction temperature controls between 80 ~ 120 DEG C, and the sulfonation reaction time is 3.0 ~ 6.0h, obtains sulfonated products methylene-succinic acid sodium sulfonate solution; Cooling, adds ethanol, then carries out freezing treatment to solution, obtain white precipitate in above-mentioned solution, for subsequent use after filtration, drying; Again under the effect of an acidic catalyst, methylene-succinic acid sodium sulfonate and n-Octanol is made to carry out esterification, esterification reaction temperature 110 ~ 180 DEG C, reaction time of esterification is 2.0 ~ 6.0h, cooling after esterification completes, obtain product methylene-succinic acid di-n-octyl sulfonate sodium by washing with alcohol, product ultimate yield is 90.0% ~ 98.5%.
Said an acidic catalyst is phosphoric acid.Remaining with embodiment 1.
Embodiment 6
The preparation method of methylene-succinic acid di-n-octyl sulfonate sodium, its material proportion is:
1) mass ratio of sodium bisulfite and methylene-succinic acid is 0.85/1;
2) mass ratio of hydroquinone of polymerization retarder and methylene-succinic acid is 0.02%;
3) mass ratio of an acidic catalyst and methylene-succinic acid is 2.0%;
4) mass ratio of n-Octanol and methylene-succinic acid sodium sulfonate is 1.2/1.
0.005g Resorcinol, 26.0g methylene-succinic acid is added in the reaction vessel with agitator, thermometer, prolong.22.1g sodium bisulfite is dissolved in 51.6g deionized water, then dropwise joins in reaction vessel.Control sulfonation temperature 120 DEG C reaction 6.0h, obtain sulfonated products methylene-succinic acid sodium sulfonate solution; Be down to room temperature, in solution, add 50.0mL dehydrated alcohol, then carry out freezing treatment, obtain white precipitate, for subsequent use after filtration, drying; Taking 0.5g tosic acid, 46.8g methylene-succinic acid sodium sulfonate and 56.2g n-Octanol is put in the reaction vessel with agitator, thermometer, prolong, control esterification temperature 110 DEG C reaction 6.0h, react rear cooling, obtain product methylene-succinic acid di-n-octyl sulfonate sodium by washing with alcohol, product yield is 93.2%.
embodiment 7
The preparation method of methylene-succinic acid di-n-octyl sulfonate sodium, its material proportion is:
1) mass ratio of sodium bisulfite and methylene-succinic acid is 0.85/1;
2) mass ratio of hydroquinone of polymerization retarder and methylene-succinic acid is 0.04%;
3) mass ratio of an acidic catalyst and methylene-succinic acid is 4.0%;
4) mass ratio of n-Octanol and methylene-succinic acid sodium sulfonate is 1.2/1.
0.01g Resorcinol, 26.0g methylene-succinic acid is added in the reaction vessel with agitator, thermometer, prolong.22.1g sodium bisulfite is dissolved in 51.6g deionized water, then dropwise joins in reaction vessel.Control sulfonation temperature 80 DEG C reaction 3.0h, obtain sulfonated products methylene-succinic acid sodium sulfonate solution; Be down to room temperature, in solution, add 50.0mL dehydrated alcohol, then carry out freezing treatment, obtain white precipitate, for subsequent use after filtration, drying; Taking the 1.0g vitriol oil, 46.8g methylene-succinic acid sodium sulfonate and 56.2g n-Octanol is put in the reaction vessel with agitator, thermometer, prolong, control esterification temperature 140 DEG C reaction 4.0h, react rear cooling, obtain product methylene-succinic acid di-n-octyl sulfonate sodium by washing with alcohol, product yield is 90.7%.
embodiment 8
The preparation method of methylene-succinic acid di-n-octyl sulfonate sodium, its material proportion is:
1) mass ratio of sodium bisulfite and methylene-succinic acid is 0.85/1;
2) mass ratio of hydroquinone of polymerization retarder and methylene-succinic acid is 0.04%;
3) mass ratio of an acidic catalyst and methylene-succinic acid is 4.0%;
4) mass ratio of n-Octanol and methylene-succinic acid sodium sulfonate is 2.0/1.
0.01g Resorcinol, 26.0g methylene-succinic acid is added in the reaction vessel with agitator, thermometer, prolong.22.1g sodium bisulfite is dissolved in 51.6g deionized water, then dropwise joins in reaction vessel.Control sulfonation temperature 95 DEG C reaction 6.0h, obtain sulfonated products methylene-succinic acid sodium sulfonate solution; Be down to room temperature, in solution, add 50.0mL dehydrated alcohol, then carry out freezing treatment, obtain white precipitate, for subsequent use after filtration, drying; Taking 1.0g tosic acid, 46.8g methylene-succinic acid sodium sulfonate and 56.2g n-Octanol is put in the reaction vessel with agitator, thermometer, prolong, control esterification temperature 180 DEG C reaction 2.0h, react rear cooling, obtain product methylene-succinic acid di-n-octyl sulfonate sodium by washing with alcohol, product yield is 92.1%.
embodiment 9
The preparation method of methylene-succinic acid di-n-octyl sulfonate sodium, its material proportion is:
1) mass ratio of sodium bisulfite and methylene-succinic acid is 0.85/1;
2) mass ratio of hydroquinone of polymerization retarder and methylene-succinic acid is 0.05%;
3) mass ratio of an acidic catalyst and methylene-succinic acid is 2.0%;
4) mass ratio of n-Octanol and methylene-succinic acid sodium sulfonate is 1.2/1.
0.01g Resorcinol, 26.0g methylene-succinic acid is added in the reaction vessel with agitator, thermometer, prolong.22.1g sodium bisulfite is dissolved in 51.6g deionized water, then dropwise joins in reaction vessel.Control sulfonation temperature 95 DEG C reaction 4.5h, obtain sulfonated products methylene-succinic acid sodium sulfonate solution; Be down to room temperature, in solution, add 50.0mL dehydrated alcohol, be then placed in refrigerator and cooled and freeze process, obtain white precipitate, for subsequent use after filtration, drying; Taking 1.0g tosic acid, 46.8g methylene-succinic acid sodium sulfonate and 56.2g n-Octanol is put in the reaction vessel with agitator, thermometer, prolong, control esterification temperature 140 DEG C reaction 4.0h, react rear cooling, obtain product methylene-succinic acid di-n-octyl sulfonate sodium by washing with alcohol, product yield is 98.5%.
Above-described embodiment take methylene-succinic acid as starting raw material, the synthesis technique of esterification after employing earlier sulfonation, successfully solve the problem that in traditional sulfonation reaction process, esterification products (oil soluble) is immiscible with sulphonating agent (water-soluble) two-phase, two-step reaction is all completed in homogeneous system, avoid the use of phase-transfer catalyst, simplify production process route, improve product purity and yield.The methylene-succinic acid di-n-octyl sulfonate sodium product yield prepared according to synthesis technique of the present invention is high, can be used as lubricant, permeate agent etc.
Above-described embodiment is explained in detail the present invention, but the present invention is not limited in above-described embodiment, in the ken that those of ordinary skill in the art possess, can also make many variations to it.Such as, when carrying out purifying to sulfonated products methylene-succinic acid sodium sulfonate, also can select other conventional organic solvent, as acetone, desirable separating effect can also be reached.
Claims (5)
1. a methylene-succinic acid di-n-octyl sulfonate sodium, it is characterized in that it be a kind of with methylene-succinic acid, sodium bisulfite and n-Octanol for raw material, respectively under the effect of stopper and an acidic catalyst, be prepared from through sulfonation reaction and esterification, there is following molecular structure:
。
2. according to the preparation method of methylene-succinic acid di-n-octyl sulfonate sodium according to claim 1, it is characterized in that it take water as solvent, take Resorcinol as stopper, be that sulphonating agent carries out sulfonation to methylene-succinic acid with sodium bisulfite, obtain sulfonated products methylene-succinic acid sodium sulfonate solution, after being separated, purifying, obtain methylene-succinic acid sodium sulfonate white powder; Again under the effect of an acidic catalyst, adopt n-Octanol and methylene-succinic acid sodium sulfonate to carry out esterification, after cooling, obtain methylene-succinic acid di-n-octyl sulfonate sodium through washing with alcohol.
3., according to the preparation method of methylene-succinic acid di-n-octyl sulfonate sodium according to claim 2, it is characterized in that the material proportion reacted is:
1) mass ratio of sodium bisulfite and methylene-succinic acid is 0.8/1 ~ 1.0/1;
2) mass ratio of hydroquinone of polymerization retarder and methylene-succinic acid is 0.01% ~ 0.1%;
3) mass ratio of an acidic catalyst and methylene-succinic acid is 1.0% ~ 5.0%;
4) mass ratio of n-Octanol and methylene-succinic acid sodium sulfonate is 1.1/1 ~ 2.5/1.
4. according to the preparation method of methylene-succinic acid di-n-octyl sulfonate sodium according to claim 2, it is characterized in that its preparation technology adopts rhythmic reaction mode, take water as solvent, under the effect of stopper, methylene-succinic acid and sodium bisulfite is made to carry out sulfonation reaction, sulfonation reaction temperature controls between 80 ~ 120 DEG C, and the sulfonation reaction time is 3.0 ~ 6.0h, obtains sulfonated products methylene-succinic acid sodium sulfonate solution; Cooling, adds ethanol, then carries out freezing treatment to solution, obtain white precipitate in above-mentioned solution, for subsequent use after filtration, drying; Again under the effect of an acidic catalyst, methylene-succinic acid sulfonated products and n-Octanol is made to carry out esterification, esterification reaction temperature 110 ~ 180 DEG C, reaction time of esterification is 2.0 ~ 6.0h, cooling after esterification completes, obtain methylene-succinic acid di-n-octyl sulfonate sodium through washing with alcohol, the ultimate yield of product is 90.0% ~ 98.5%.
5., according to the preparation method of methylene-succinic acid di-n-octyl sulfonate sodium according to claim 2, it is characterized in that described an acidic catalyst is the vitriol oil, hydrochloric acid, phosphoric acid, tosic acid.
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| CN110669595A (en) * | 2019-10-23 | 2020-01-10 | 上海源育节能环保科技有限公司 | Automobile polishing cleaning agent and preparation method thereof |
| CN110684607A (en) * | 2019-10-23 | 2020-01-14 | 上海源育节能环保科技有限公司 | Environment-friendly cleaning agent and preparation method thereof |
| CN111747871A (en) * | 2020-07-31 | 2020-10-09 | 潍坊市埃里特化学有限公司 | Production process of surfactant dioctyl sodium sulfosuccinate |
| CN113121494A (en) * | 2021-04-13 | 2021-07-16 | 荣成青木高新材料股份有限公司 | Process for the preparation of beta-sulfopropionic anhydride |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110669595A (en) * | 2019-10-23 | 2020-01-10 | 上海源育节能环保科技有限公司 | Automobile polishing cleaning agent and preparation method thereof |
| CN110684607A (en) * | 2019-10-23 | 2020-01-14 | 上海源育节能环保科技有限公司 | Environment-friendly cleaning agent and preparation method thereof |
| CN111747871A (en) * | 2020-07-31 | 2020-10-09 | 潍坊市埃里特化学有限公司 | Production process of surfactant dioctyl sodium sulfosuccinate |
| CN113121494A (en) * | 2021-04-13 | 2021-07-16 | 荣成青木高新材料股份有限公司 | Process for the preparation of beta-sulfopropionic anhydride |
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